Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 15, Issue 41, Pages 10997-11009Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200900728
Keywords
density functional calculations; electrochemistry; fullerenes; HOMO-LUMO gap; metal nitride clusters
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Funding
- Spanish Ministry of Science and Technology [cTQ2008-06549-C02-01/BQU, CTQ2008-06644-C0201]
- DURSI of the Generalitat de Catalunya [2005SGR-00104]
- Catalan Government (Generalitat de Catalunya)
- National Science Foundation [CHE-0509989]
- National Science Foundation
- ICREA Funding Source: Custom
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An extensive study of the redox properties of metal nitride endohedral fullerenes (MNEFs) based on DFT computational calculations has been performed. The electronic structure of the singly oxidized and reduced MNEFs has been thoroughly analyzed and the first anodic and cathodic potentials, as well as the electrochemical gaps, have been predicted for a large number of M3N@C-2n Systems (M=Sc, Y, La, and Gd; 2n = 80, 84, 88, 92, and 96). In particular, calculations that include thermal and entropic effects correctly predict the different anodic behavior of the two isomers (I-h and D-5h) of Sc3N@C-80, which is the basis for their electrochemical separation. Important differences were found in the electronic structure of reduced M3N@C-80 when M = Sc or when M is a more electropositive metal, such as Y or Gd. Moreover, the changes in the electrochemical gaps within the Gd3N@C-2n series (2n=80, 84, and 88) have been rationalized and the use of Y-based computational models to study the Gd-based systems has been justified. The redox properties of the largest MNEFs characterized so far, La3N@C-2n (2n=92 and 96), were also correctly predicted. Finally, the quality of these predictions and their usefulness in distinguishing the carbon cages for MNEFs with unknown structures is discussed.
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